Son paul hulin



(No Model.)

L. P. HULIN. ELEGTROLYTIG PROCESS AND APPARATUS. No. 542,057. Patented July 2, 1895.

UNrTan STATES PATENT @rrion,

LEON PAUL HULIN, OF MODANE, FRANCE.

ELECTROLYTIC PROCESS AND APPARATUS.

SPECIFICATION forming part of Letters Patent No. 542,057, dated July 2, 1895.

Application filed December 19, 1894. Serial No. 532,291. (No model.) Patented in Trance May 5, 1894, No. 238,301, and in Belgium May 5,1894,No. 109,791.

To all whom it may concern.-

Be it known that I, LEON PAUL HULIN, of the city of Modane, (Savoy,) France, have invented an Improved Electrolytic Process and Apparatus for Obtaining Rich Alloys of the Metals of the Alkali or Alkali Earths andthe Production of Halogen Elements, (for which I have Obtained Letters Patent in France for fifteen years, dated May 5, 1894, No. 238,301,

and in Belgiumfor fifteen years, dated May.

5, 1894:, No. 109,791,) of which the following is a full, clear, and exact description.

This invention relates to an electrolytic pro- 1 cess and apparatus for obtaining rich alloys of the metals of the alkalies or alkali earths,

together with the production of halogen ele ments.

In order to produce by electrolysis alloys formed of a heavy metal and of a very light metal, the method generally employed'in the case of aluminium, magnesium, &c., consists in electrolyzing a haloid compound of light metal in a state of igneous fusion with a cathode of the heavy metal in a molten or,

highly-heated condition. This method does not permit of readily obtaining all the alloys of the light metals with certain heavy metals which are diffionltly fusible and which in the alloy my process consists in the conjoint employment of two anodes acting in the same bath, which is expressly constituted by a haloid salt of the alkali metal, (fluoride, chloride, bromide,) in astate of igneous fusion. One of the anodes is of carbon and the other is formed by the heavy metal which is to enter into the alloy. Each of the anodes receives a quantity of the positive current which is determined andregulated in conformity with tive pole some of the alkali metal and of the heavy metal, and the latter meeting the other in the nascent state becomes completely incorporated therewith to form an alloy of greater density than the electrolyte and which remains at the bottom of the apparatus. Although the haloid compound of the heavy metal is much more readily electrolyzable than the alkali compound, the latter will always be decomposed, as it alone forms almost the whole of the bath into which the other enters only in proportion as its anode is attacked, which attack corresponds only to that part of the total current which has been allotted'for the purpose. The-quantity of positive current passing by the carbon anode corresponds to the quantity of alkali metal liberated,and the quantity of positive current'pass-l ing by the metallic anode corresponds to the quantity of heavy metal to be united with the alkali metal. It is evident that these quantities of the respective metals are proportionate to their electrochemicalequivalents. One single cathode receives all the negative current. The composition of the alloy is thus governed by the distribution of the positive current through the anodes. For this purpose the metallic anode is combined with a resistance which may be variable at will, and, if necessary, with an ampere-meter. No resistance is necessary for the carbon anode.

' It will be seen that the halogen element produced by electrolysis byjmy method is set free in part as a conjoint product with the alloy, while the other part is utilized for dissolving the heavy metal in the alkali bath. The attack on the metallic anode diminishes the counter electromotive force in its branch circuit, and it is for this reason that a resistance is hereeu'sed. There is a consequent loss of electric energy, it istrue, which may, however, be av ided, if desired,by employing two independent sources of electricity having a different voltage capable of being varied and regulated at will, in which case the two negative poles of these two sources are connected with the cathode, while the two positive poles are connected separately, the one to the carbon anode and the other and weaker one to the metallic anode, without the interposition of resistance, the ampere-meter being retained. The proper may be supplied to each anode by passing the current alternately to one and the other for calculated periods or continuously to the carbon anode and intermittently to the metallic anode; but these variations are of little practical value.

It will be evident that in all cases the whole of the negative current is conducted to the cathode, where the alkali metal and the heavy metal unite in a nascent state. The metallic anodes employed are generally in the form of rods or bars of any section. In the case of certain metals, such as manganese, chromium, 850., which are difficult to obtain in a metallic state, I employ in place of the metalproperly so called rods composed of an intimate mixture of an oxide of these metals with suitable quantities of carbon, the nascent halogen element (fluorine, chlorine, bromine) thus combining with the metal of the oxide and setting I free carbonic oxide. If it is desired to form alloys with heavy metals fusible at the temperature at which the electrolysis is performed, I employ for this purpose a special support composed of a rod of carbon provided at bottom with a shallow vessel, which may be of the same material and formed in one therewith, in which vessel is deposited fusible metal which is immersed in the alkaline bath, the rod projecting upward and being suitably connected to the positive pole, as before mentioned. The vessel may also be supplied with slightly-fusible metal in a granulated form or pieces of agglomerated oxide and carbon. When it is desired to form alloys of more than two heavy metals, the operation is always performed under the same conditions and accord ing to the same principles; but in this case I employ as many anodes combined with a resistance of suitable value as there are metals to enter into the final alloy, except when several of these metals may have been previously united in the desired proportions to form a single anode. By composing the bath of a mixture of two alkaline haloidsin the desired proportions I am enabled to obtain the two alkali metals in the alloy.

It will be evident that each kind of anode (whether of carbon or metal) may be formed of several parts, rods, sticks, or vessels, &c., electrically connected in a group or acting as one.

The feeding of my system thus comprises, first, the replacement of the metallic anodes for the heavy metal; second, the addition of the haloid salt of an alkali in the bath in fuuantity of electricity sion for the alkali metal. Thus constituted, my process furnishes in addition to the alloy a halogen element (generally chlorine) which is collected on leaving the apparatus for utilization in any known way. It may first be caused to pass through condensing-chambers, where it will separate from any alkaline salt that may have been carried off along with it by volatilization. It may also be washed with the same object.

The accompanying drawing represents, by way of example, a section of the essential parts of the apparatus employed, which is susceptible of modification as regards dimensions, form, and accessory details, and especially in the relative position of the anodes.

A is a wrought or cast iron or steel crucible provided with an insulating-lining S in which the whole operation is performed. In order to melt the alkaline salt, at least at the outset of the operation, the vessel may be placed over a furnace.

B is the alkaline bath in igneous fusion, chloride of'sodium, for example.

0 is the outlet-pipe for the free halogen element-chlorine, for example.

D is a cover of insulating refractory material, down through which pass the electrodes, the joints being made as light as possible.

E is the outlet at bottom for running off the alloy formed.

F is the valve, and G the receiver, for the alloy extracted.

H is an inclined lateral dip-pipe, the lower end of which is completely immersed in the molten bath, which permits of continuously supplying the alkaline salt without opening the chamber I in which the chlorine is contained, thus preventing all loss and smell.

J is the carbon electrode at which the halo gen element is set free. It may, if necessary, be suspended from a metal rod N.

K K represent a metallic anode made in two parts formed of rods of iron for example.

L is a dish-shaped anodesupport of carbon containing heavy metal in a molten state, such as tin, lead, 850., which may be introduced through the hollow supporting-rod, which passes out at top, two holes an opening laterally from the bore near the bottom of the dish Mj.

Mk M Z represent the metallic supports for the anodes. Theyserve as conductors for the positive current after its division and are provided with binding-screw for insuring contact and enabling the anodes to be raised or lowered at will.

O, 0 7c, 0 Z are am pere-meters, whereby the intensity of the current. in each of the three anodes is controlled.

P 70, P Zare two variable resistances, each combined with an ampere-meter and a metallic anode, and by means of which the distribution of the current in the anodes is effected.

Q R are the two main conductors leading from the electric source, (here considered as single,) the negative conductor B being in contact with the crucible A, of which the bottom forms the cathode.

T is the alkali alloy produced.

Visa stirrer, usually made of iron, mounted on a vertical axis, which is employed when it is desired to manufacture an unstable alloy, such as those of metals having little or no mutual afinity. By means of this stirrer, which may beoperated bymechanical means, the homogeneity of the alloy is maintained throughout the entire operation.

My process entirely solves the difficulties in the electrolysis of molten alkali salts,partr'cularly chlorides. I avoid in fact the diffusion of the alkali metal in the electrolyte by incorporating it in a nascent state with a heavy metal also in the nascent state.

When the operation of forming the alloy has only for its object to obtain the alkali metal, I select a heavy metal whose electrochemical equivalent and density are high in order to give the alloy sufiicient density While consuming a minimum of electric current a the metalic anode.

The description of my process of making alloys of the alkalies and the essential organization of the apparatus by means of which it is applied will enable my invention to be clearly understood. Although the anodes L K K are shown as placed at one time in the crucible A, this is simply for the purpose of describing them,as it willbe evident that one may be used without the other, or more anode members may be used, an unused opening being shown as closed by plug U. The position and form of the cathode may be those of any of the known arrangements.

I claim-'- 1. The process of manufacturing an alloy of an alkali metal or alkali earth metal with a heavy metal, which consists in efiecting the electrolysis of a suitable haloid salt of an alkali or alkali earth metal when in a state of igneous fusion, by means ot' two anodes, one of carbon, and the other formed of the heavy metal to bealloyed.

2. The herein described method of manufacturing alloys by electrolysis, which consists in employing as an electrolyte thefused salts of the metal of one ingredient of the proposed alloy, and an anode comprised of a carbon member and a metal member composed of the other ingredient for the proposed alloy, as specified.

3. The herein described method of mann facturinga-lloyswhich consists in employing as an .electrolyte the fused saltsof one metal of the alloy and an anode consisting of a carbon member and-a member composed of the other metal of the alloy and varying the current to regulate the composition of the alloy, asspecified.

4. In apparatus for the production of alloys by electrolysis, the combination of a cathode consisting of ametal crucible, adapted to contain an electrolyte, provided with insulated sides and an exposed bottom, an anode consisting of a carbon and one or more metal members and a stirrer in the crucible, substantially as described.

5. In apparatus for the production of alloys by electrolysis the combination with a bath and cathode, an anode consisting of a carbon member and a dish-shaped metal receiving member provided with a hollow stem having lateral openings, communicating with the dish, substantially as described.

6. In apparatus for the production of alloys by electrolysis, an anode-metal container consistlng of a dish provided with a hollow stem having lateral openings communicating with the dish, substantially as described.

'7. In apparatus for the production of alloys by electrolysis, an anode consisting of a carbon member, and metal members comprised of one or more rods and a dish-shaped metalcontainer provided with a hollow stem having lateral openings communicating with the dish, substantially as described.

The foregoing specification of my improved electrolytic process and apparatus for obtaining rich alloys of the metals of the alkali or alkali earths and the production of halogen elements signed by me this 3d day of December, 1894.

- LEON PAUL HULIN.

Witnesses:

CLYDE SHROPSHIRE, ALBERT MOREAU. 

